This work presents study of magnetocaloric properties of compounds exhibiting unusual magnetic characteristics. Several systems were studied: TbNiAl, (Tb,Y)NiAl, TbNi(Al,In), TbFeAl, GdFeAl, Ni2MnGa based compounds and amorphous metallic alloy Gd-Co-Al-Y. Influence of magneto-crystalline anisotropy on magnetocaloric effect was studied on singlecrystalline sample of TbNiAl compound. The maximum of entropy change was measured with orientation of magnetic field along c axis and compared to polycrystalline sample a 100% increase was observed. Substitutions of Y and In in TbNiAl led to a change of magnetic ordering. Both substitution led to increase of RCP values of studied material. TbFeAl and GdFeAl compounds, characterized by partial disorder of Fe and Al atoms, showed magnetocaloric effect in wide temperature region which led to interesting values of RCP~350 J kg-1 . Very broad region of magnetocaloric effect was also observed on amorphous metallic material of Gd-Co-Al-Y. The effect of Er substitution in Ni2MnGa based compound on its magneto-structural transition, connected with inverse magnetocaloric effect, was studied. The direct measurement method of adiabatic temperature change is described and instrument for such measurement, developed in collaboration with FZU AVČR, v.v.i., is presented.

Deux séries d'échantillon à base de PVDF ont été élaborées avec différentes fractions de dioxyde de titane TiO2 en utilisant deux modes d'élaboration : dispersion des nanoparticules de TiO2 par voie fondue habituelle et génération des charges de TiO2 basée sur des réactions d'hydrolyse-condensations d'un alkoxyde de titane (le n-tétrabutoxyde de titane). Dans cette étude, quatre techniques ont été utilisées pour étudier les processus de relaxation dans les polymères semi-cristallins. Le microscope électronique à balayage (MEB) pour étudier la dispersion des nanoparticules de TiO2 dans la matrice PVDF. La calorimétrie différentielle à balayage (DSC) a été utilisée dans cette étude pour caractériser thermiquement les échantillons polymériques semi-cristallins. L'analyse thermo-gravimétrique (ATG) a été utilisée pour voir l'effet de nanoparticules sur les propriétés thermiques du PVDF. De plus, la technique de spectroscopie diélectrique a été utilisée dans la thèse pour étudier l'influence du processus d'élaboration sur la mobilité moléculaire trouvée dans ces systèmes. On a montré que le comportement de ces nanocomposites est proche de celui de PVDF pur. Les changements principaux observés sont le ralentissement de la dynamique de la relaxation alpha (associée à la température de transition vitreuse) et la relaxation alpha c (associée à la phase cristalline) en fonction de l'augmentation de fraction volumique TiO2. L'existence des charges piégées aux interfaces qui met en cause la présence de la polarisation interfaciale (IP) dans les différents nanocomposites a aussi été analysée. Les additions de TiO2 diminuent la mobilité des chaînes polymériques ce qui rend difficile l'orientation des dipôles électriques et augmente l'énergie d'activation de la relaxation de polarisation interfaciale / Polyvinylidene fluoride (PVDF) films have been filled with different volume fraction of titanate dioxide TiO2 using two ways : dispersion in the melt or in-situ generation based on the hydrolysis-condensation reactions of titanium alkoxide inorganic precursor premixed with PVDF under molten conditions. In this study, four techniques were used to study the relaxation processes in the semi-crystalline polymers. The scanning electron microscope (SEM) was introduced in the field of polymer science to study the dispersion of TiO2 nanoparticules in the PVDF matrix. The differential scanning calorimetry (DSC) was used in this study to thermally characterize the semi-crystalline polymer samples. Thermal gravimetric analysis (TGA) was used to see the effect of nanoparticles on the thermal properties of PVDF. In addition, the dielectric spectroscopy technique was used in the thesis to study the influence of the process on the molecular mobility found in these systems. It was shown that the behavior of PVDF as a matrix in these nanocomposite is close to that of pure PVDF. The main changes observed is the slowing down of the dynamics of the alpha a (associated to the glass transition temperature) and the alpha c (associated to the crystalline phase) relaxations as a function of the TiO2 volume fraction increase. The existence of charge carriers trapping at the interfaces related to the interfacial polarization (IP) in the different nanocomposites has also been analyzed. The additions of TiO2 decrease the mobility of the polymer chains which makes difficult the orientation of electric dipole moment ending in an increase of the energy of activation of IP relaxation

Molecular reinforcement through in-situ polymerization of liquid crystalline epoxies (LCEs) and a non-liquid crystalline epoxy has been investigated. Three LCEs: diglycidyl ether of 4,4'-dihydroxybiphenol (DGE-DHBP) and digylcidyl ether of 4-hydroxyphenyl-4"-hydroxybiphenyl-4'-carboxylate (DGE-HHC), were synthesized and blended with diglycidyl ether of bisphenol F (DGEBP-F) and subsequently cured with anhydride and amine curing agents. Curing kinetics were determined using differential scanning calorimetry (DSC). Parameters for autocatalytic curing kinetics of both pure monomers and blended systems were determined. The extent of cure for both monomers was monitored by using Fourier transform infrared spectroscopy (FT-IR). The glass transitions were evaluated as a function of composition using DSC and dynamic mechanical analysis (DMA). The results show that the LC constituent affects the curing kinetics of the epoxy resin and that the systems are highly miscible. The effects of molecular reinforcement of DGEBP-F by DGE-DHBP and DGE-HHC were investigated. The concentration of the liquid crystalline moiety affects mechanical properties. Tensile, impact and fracture toughness tests results are evaluated. Scanning electron microscopy of the fracture surfaces shows changes in failure mechanisms compared to the pure components. Results indicate that mechanical properties of the blended samples are improved already at low concentration by weight of the LCE added into epoxy resin. The improvement in mechanical properties was found to occur irrespective of the absence of liquid crystallinity in the blended networks. The mechanism of crack study indicates that crack deflection and crack bridging are the mechanisms in case of LC epoxy. In case of LC modified epoxy, the crack deflection is the main mechanism. Moreover, the effect of coreacting an epoxy with a reactive monomer liquid crystalline epoxy as a matrix for glass fiber composites was investigated. Mechanical properties of the modified matrix were determined by tensile, flexural and impact testing. The improvement in toughness of the bulk matrix by the addition of a LCEs is seen also in the composites. The improvement is related to the enhancement of adhesion between the glass fibers and the matrix.

Water resources in hard rock terrain are difficult to characterize due to heterogeneity and anisotropy in the fracture network, low porosities and limited recharge volumes available during the summer season. Three methods were developed and evaluated in order to assist in water supply planning. A groundwater resources potential index was estimated using multivariate statistics, where physical and geological variables were classified using Analysis of Variance and Fisher's Least Significant Difference tests according to their effect on hydraulic properties. Principal component analysis was used to assign weights to the different classed variables. Classes and weights were used to produce an index referred to as groundwater resources potential (GRP), which correlated significantly with well data. Nearly 80% of the wells with less than median specific capacity values also had GRP values at those locations of zero or lower. Non-stationary variance was observed in specific capacity sub-samples taken from the Geological Survey of Sweden's well archive, despite homogeneous geology and topography. Spatial statistical analyses showed that spatial correlations were weak in well archive samples, implying that regional approximations based on sparse point data are highly error prone. Kinematic porosity estimated using superficial fracture measurements correlated significantly with well archive data. However, low correlation coefficients indicated that well data is likely not a suitable method for predicting water supply characteristics. This approach is an efficient method which shows promise in preliminary estimations of groundwater storage in heterogenic terrains. A groundwater balance model which describes seasonal groundwater storage changes was created in order to better approximate the groundwater situation often found in Swedish urbanized and semi-urbanized hard rock terrains. The model was based on a water budget approach at the pixel scale, and allows for approximation of well extraction which is not uniformly distributed in space. The model showed that in specific regions groundwater extraction may lead to severe decreases in groundwater level, where these impacts may not otherwise be expected. Dry season modelling with 10% increased evapotranspiration showed that in several areas groundwater reservoir depletion may be influenced by more than 50%. / <p>QC 20140331</p>

The compacted bentonites are used as buffer and backfill materials for engineering barriers for high-level nuclear waste repositories located underground. For this purpose, it is very important to evaluate the swelling characteristics of this clay. The swelling capacity is one of the most important properties of the bentonite clay. The swelling behaviour is due two mechanisms, the crystalline swelling and the osmotic swelling. These mechanisms produce an increase in the distance between the layers of montmorillonite which is one component of bentonite. The result of the swelling capacity is the swelling pressure. It has been studied in several investigations. The results of experimental tests have been collected and compared in this thesis, considering only the Na-dominant bentonite and sand and distilled water as test solution. The experimental tests show that there is only an unique relation between different bentonites in the Na-dominant bentonite and sand mixture swollen depending on its final dry density. Also, the relation between the swelling pressure and the clay void ratio shows the mechanism of the swelling pressure. On the other hand, a mechanistic model is used to predict the swelling pressure of fully saturated bentonite and sand mixture in distilled water. Firstly, it has been compared with the results of experimental tests and it should be pointed out that the model gives good predictions. In addition, the model has been used to make sensitivity analysis with different parameters of bentonite. The most important conclusions in this section show that the swelling pressure mainly depends on the distance among particles. Also, the sensitivity analyses indicate which parameters should be fitted more carefully for future studies to validate this model with different bentonites.

This study evaluates the pre-treatment of cellulose from kenaf plant to yield sugar precursors for the production of ethanol or butanol for use as biofuel additives. In order to convert the crystalline cellulosic form to the amorphous form that can undergo enzymatic hydrolysis of the glycosidic bond to yield sugars, kenaf pulp samples were subjected to two different pre-treatment processes. In the acid pre-treatment, the pulp samples were treated with 37.5% hydrochloric acid in the presence of FeCl 3 at 50 °C or 90 °C whereas in the alkaline method, the pulp samples were treated with 25% sodium hydroxide at room temperature and with 2% or 5% sodium hydroxide at 50 °C. Microwave-assisted NaOH-treatment of the cellulose was also investigated and demonstrated to be capable of producing high glucose yield without adverse environmental impact by circumventing the use of large amounts of concentrated acids i.e., 83-85% phosphoric acid employed in most digestion processes. The treated samples were digested with the cellulase enzyme from Trichoderma reesei. The amount of glucose produced was quantified using the QuantichromTMglucose bioassay for assessing the efficiency of glucose production for each of the treatment processes. The microwave-assisted alkaline pre-treatment processes conducted at 50 °C were found to be the most effective in the conversion of the crystalline cellulose to the amorphous form based on the significantly higher yields of sugar produced by enzymatic hydrolysis compared to the untreated sample.

Au cours de cette thèse, j’ai étudié la possibilité et les avantages d’utiliser des contacts nanométriques au-dessous de 1 µm. Des simulations analytiques et numériques ont montré que ces contacts nanométriques sont avantageux pour les cellules en silicium cristallin comme ils peuvent entrainer une résistance ohmique négligeable. Mon travail expérimental était focalisé sur le développement de ces contacts en utilisant des nanoparticules de polystyrène comme un masque. En utilisant la technique de floating transfert pour déposer les nanosphères, une monocouche dense de nanoparticules s’est formée. Cela nécessite une gravure par plasma de O2 afin de réduire la zone de couverture des NPs. Cette gravure était faite et étudiée en utilisant la technique de plasmas matriciels distribués à résonance cyclotronique électronique (MD-ECR). Une variété de techniques de créations de trous nanométriques était développée et testée dans des structures de couches minces et silicium cristallin. Des trous nanométriques étaient formés dans la couche de passivation, de SiO2 thermique, du silicium cristallin pour former des contacts nanométriques dopés. Un dopage local de bore était fait, à travers ces trous nanométriques par diffusion thermique et implantation ionique. En faisant la diffusion, le dopage local était observé par CP-AFM en mesurant des courbes de courant-tension à l’intérieur et à l’extérieur des zones dopées et en détectant des cellules solaires nanométriques. Par contre le processus de dopage local par implantation ionique a besoin d’être améliorer afin d’obtenir un résultat similaire à celui de diffusion. / The use of point contacts has made the Passivated Emitter and Rear Cell design one of the most efficient monocrystalline-silicon photovoltaic cell designs in production. The main feature of such solar cell is that the rear surface is partially contacted by periodic openings in a dielectric film that provides surface passivation. However, a trade-off between ohmic losses and surface recombination is found. Due to the technology used to locally open the contacts in the passivation layer, the distance between neighboring contacts is on the order of hundreds of microns, introducing a significant series resistance.In this work, I explore the possibility and potential advantages of using nanoscale contact openings with a pitch between 300 nm to 10 µm. Analytic and numerical simulations done during the course of this thesis have shown that such nanoscale contacts would result in negligible ohmic losses while still keeping the surface recombination velocity Seff,rear at an acceptable level, as long as the recombination velocity at the contact (Scont) is in the range from 103-105 cm/s. To achieve such contacts in a potentially cost-reducing way, my experimental work has focused on the use of polystyrene nanospheres as a sacrificial mask.The thesis is therefore divided into three sections. The first section develops and explores processes to enable the formation of such contacts using various nanosphere dispersion, thin-film deposition, and layer etching processes. The second section describes a test device using a thin-film amorphous silicon NIP diode to explore the electrical properties of the point contacts. Finally, the third section considers the application of such point contacts on crystalline silicon by exploring localized doping through the nanoholes formed.In the first section, I have explored using polystyrene nanoparticles (NPs) as a patterning mask. The first two tested NPs deposition techniques (spray-coating, spin-coating) give poorly controlled distributions of nanospheres on the surface, but with very low values of coverage. The third tested NPs deposition technique (floating transfer technique) provided a closely-packed monolayer of NPs on the surface; this process was more repeatable but necessitated an additional O2 plasma step to reduce the coverage area of the sphere. This was performed using matrix distributed electron cyclotron resonance (MD-ECR) in order to etch the NPs by performing a detailed study.The NPs have been used in two ways; by using them as a direct deposition mask or by depositing a secondary etching mask layer on top of them.In the second section of this thesis, I have tested the nanoholes as electrical point-contacts in thin-film a-Si:H devices. For low-diffusion length technologies such as thin-film silicon, the distance between contacts must be in the order of few hundred nanometers. Using spin coated 100 nm NPs of polystyrene as a sacrificial deposition mask, I could form randomly spaced contacts with an average spacing of a few hundred nanometers. A set of NIP a-Si:H solar cells, using RF-PECVD, have been deposited on the back reflector substrates formed with metallic layers covered with dielectrics having nanoholes. Their electrical characteristics were compared to the same cells done with and without a complete dielectric layer. These structures allowed me to verify that good electrical contact through the nanoholes was possible, but no enhanced performance was observed.In the third section of this thesis, I investigate the use of such nanoholes in crystalline silicon technology by the formation of passivated contacts through the nanoholes. Boron doping by both thermal diffusion and ion implantation techniques were investigated. A thermally grown oxide layer with holes was used as the doping barrier. These samples were characterized, after removing the oxide layer, by secondary electron microscopy (SEM) and conductive probe atomic force microscopy (CP-AFM).

This thesis presents a 40Ar/39Ar geochronological analyses of biotite from thin ductile shear zones in Paleoproterozoic granulite-facies gneisses from the Ellesmere-Devon crystalline terrane, Nunavut, Canada. The gneisses are part of the Paleoproterozoic Thelon tectonic zone. U-Pb dates of zircon show that the gneisses have magmatic protolith ages ranging from 2007–1958 Ma. The quartzofeldspathic gneisses in southeast Ellesmere Island display centimeter-scale E- to NE-striking sinistral and dextral mylonite zones offsetting pegmatitic dikes that are the last stage of ductile deformation of the basement rocks. Samples were taken from nearshore outcrops at Hayes Fiord, Pim Island, NE of the Leffert Glacier and NW of Cape Isabella. Biotite clusters replace orthopyroxene as the result of post-granulite facies metamorphism in the gneisses. Biotite in mylonitic and ultramylonitic fabrics is found as flattened clusters and also as individual crystals defining shear bands related to mylonitization. Eight samples were dated, including biotite from five mylonites, one deformed pegmatite, one tonalite and muscovite from a pegmatite. Major element X-ray maps demonstrate that the biotite is chemically homogenous. Backscattered electron images and electron dispersive spectroscopy via scanning electron microscopy confirm that biotite lacks intercrystalline layering with other K phases. Step-heating analysis of mica at the University of Vermont yielded Paleoproterozoic 40Ar/39Ar ages. The apparent age spectra form plateau ages in all but one mylonite sample. Biotite from a protomylonite was 2051 ± 26 Ma, older than the protolith ages obtained from U-Pb zircon geochronology, and most likely indicates excess Ar. Pegmatitic muscovite was 1977 ± 35 Ma. Biotite dates range from 1874 ± 13 Ma to 1838 ± 14 Ma for the five mylonites without excess Ar. Biotite dated from ductile shear zones signals the latest deformation in the basement, which was active as early as 1887 Ma.

One portion of this work was concerned with injection molding pregenerated microcomposites composed primarily of poly(ethylene terephthalate) (PET) as the matrix and HX1000 as the thermotropic liquid crystalline polymer (TLCP). Several factors were examined to maximize the mechanical properties of these composites, including injection molding temperature, matrix viscosity, and nozzle tip exit diameter. In addition, concentrated strands of HX1000/PET (50/50 wt%) were diluted using both an injection molding grade of PET and an injection molding grade of PBT. From this work, it was determined that the best mechanical properties were produced when the microcomposites were processed at the lowest injection molding temperatures, diluted with PBT, and injection molded using a large nozzle tip exit diameter. The pregenerated microcomposite properties were compared against theoretical predictions as well as glass-filled PET. It was found that the pregenerated microcomposites had tensile moduli of approximately 70% of theoretical expectations in the machine direction. Additionally, the comparisons against glass-filled PET revealed that at the same weight fraction of reinforcement, the pregenerated microcomposites had lower properties. Still, the composites were found to have smoother surfaces than glass-filled PET and at temperatures up to 150° C the storage and loss moduli of the pregenerated microcomposites were similar to those of glass filled PET. It was concluded that if the theoretically expected levels of reinforcement could be attained, the pregenerated microcomposites processing scheme would be a viable method of producing light weight, wholly thermoplastic composites with smoother surfaces than are obtained with glass reinforcement. An additional focus of this research was to evaluate the ability to modify the crystallization behavior of a high melting TLCP (HX6000, Tm = 332° C) with a lower melting TLCP (HX8000, Tm = 272°C). It was found that it was possible to tailor the crystallization behavior of these TLCP/TLCP blends by varying the weight fraction of each component, as determined by rheological cooling scans and differential scanning calorimetric cooling tests. Based on the analysis of these TLCPs at the maximum injection molding temperature of 360° C, it was speculated that they had reacted with one another. / Ph. D.

The paper examines the work and production of Swedish ceramist Isak Isaksson (born 1949) from the aspects of emotional connection to materials, work processes, development and perceived meaning in relation to extraordinary craftmanship and the production of crystalline glazes. Isaksson has worked as a ceramist since the mid 1970s, starting with basic, functional stoneware goods but gradually moving towards the creation of art objects. His works, consisting of simple, traditional vessel shapes thrown to perfection – in combination with highly advanced crystalline glazes, have earned him recognition in Sweden and internationally.        While investigating Isaksson’s love for the intuitive, ancient technique of throwing, the paper also highlights his use of sophisticated chemical glazing methods and digital technique for creating, learning, inspiration and communication. Five of Isaksson’s contemporary pieces with crystalline glazes are studied with a combination of semiotics, associations and open senses.